The search for improved hair care products is a continual one. Since hair types vary, so do the types of products that are useful in working with different types of hair. One such product category desired by people to create a fuller appearance for their hair is known as hair volumizers. Previous attempts at adding volume to hair have involved the use of fixative-based sprays, gels or mousses to enhance styling and create volume. These products work by gluing hair together in a fixed architecture with increased volume. Such products often have the disadvantage of causing hair to be stiff or excessively sticky and do not, in general, allow the user to restyle the hair without washing out the product and reapplying it. The adhesive character of these volumizers can create difficulty in restyling. Additionally, such fixative-based products may initially cause a volumizing effect, but continued use of these products over time can result in build up on the hair resulting in loss of hair volume. The problem is magnified for people with fine hair since that type of hair is especially sensitive to being weighed down by deposits from hair care products.
The consumer wants volumizing products which are not permanent wave products, or fixative-based hair sprays or styling gels. The consumer does want a volumizing product which can add volume to otherwise flat or thin hair while maintaining some ability to restyle hair. Thus, hair volumizers as used in this context do not create a permanent architecture for the hair but allow the hair to be restyled and revolumized.
One example of a retention aid for hair styling is PCT Patent Application Publication Number WO 95/06057 to Torgerson et al. This reference describes silicone grafted thermoplastic elastomeric copolymers and hair and skin care compositions containing the same. These copolymers are useful in hair spray and mousse compositions. The copolymers described in this reference are water or alcohol soluble or dispersible thermoplastic elastomeric copolymers having a backbone and two or more hydrophilic polymeric side chains and one or more polysiloxane side chains, wherein the copolymer comprises:
(a) 20-89.9% monomer units copolymerizable with (b) and (c); PA1 (b) 10-60% hydrophilic macromonomer units having a polymeric portion and a moiety copolymerizable with (a) and (c); PA1 (c) 0.1-20% polysiloxane macromonomer units having a polymeric portion and a moiety copolymerizable with (a) and (b). PA1 (a) from 0.01-15 percent by weight (based on the total weight of the composition) of a selected liquid MQ resin having an M:Q ratio of 0.5-1.5 and a medium viscosity in the range of 1.0.times.10.sup.3 -1.times.10.sup.6 centipoise ("cps" or "cP") (for example, 0.1-10% by weight, more particularly 0.1-7.0% and, most particularly, 0.1-4%); and PA1 (b) from 85-99.99 percent by weight (based on the total weight of the composition) of a hair care carrier (also called a vehicle). PA1 (a) hydrogen, PA1 (b) phenyl, PA1 (c) phenethyl, PA1 (d) a polyether of Formula II: EQU --H.sub.2 C--(CH.sub.2).sub.n --(O--CH(R.sup.10)--CH.sub.2).sub.u --(OCH.sub.2 --CH.sub.2).sub.v --OR.sup.11 Formula II PA1 (e) C1-C24 branched and unbranched hydrocarbons optionally substituted by a halogen substituted C1-C3 hydrocarbon radical, with a particular value for R.sup.2 being C1-C24 alkyl, especially methyl; and PA1 (a) anionics as described in U.S. Pat. No. 4,902,499 to Bolich et al and U.S. Pat. No. 4,963,348 to Bolich et al both of which are incorporated by reference herein such as PA1 (b) amphoterics as described in U.S. Pat. No. 4,902,499 to Bolich et al and incorporated by reference herein such as PA1 (c) nonionic surfactants including those selected from the group described in U.S. Pat. No. 4,741,855 to Grote et all and incorporated by reference herein; these are PA1 (a) long chain fatty alcohols with greater than 14 carbons, for example C20-40, and mixtures of such long chain fatty alcohols (for example, a C&gt;14 alcohol and ethene homopolymer PETROLITE C-7138 from Petrolite Corporation, St. Louis, Mo.). PA1 (b) acrylates/steareth-20 methacrylate copolymer (for example, ACULYN.RTM. 22, from Rohm & Haas, Philadelphia, Pa.); and acrylates copolymer (for example, acrylates copolymer (ACULYN.RTM. 33); ACUSOL.RTM.-445, -810, and -830; ACRYSOL.RTM. ASE 75 from Rohm & Haas); and acrylates/C10-30 alkyl acrylate crosspolymer (PEMULENT.TM. polymeric emulsifiers from BF Goodrich Company, Brecksville, Ohio, particularly products designated as TR-1 and TR-2). For the acrylates copolymer (ACULYN.RTM. 33) product (having a pH in the range of 2.1-3.5), a neutralization step is performed with sodium phosphate (such as disodium phosphate), sodium hydroxide or a cosmetically acceptable organic amine to increase the pH to approximately 6.5. PA1 (c) agents described in U.S. Pat. No. 5,015,415 (incorporated by reference herein) especially N,N-disubstituted phthalamic acids and their ammonium salts selected from the group consisting of Formula III: ##STR4## PA1 (a) 4.00-60.00 percent of a detersive surfactant selected from the group consisting of at least one anionic detergent selected from the group consisting of C.sub.8 -C.sub.18 alkyl sulfates, C.sub.8 -C.sub.18 alkyl ethenoxy ether sulfates containing 1-5 ethenoxy groups in the molecule, C.sub.10 -C.sub.18 acyl isethionates, C.sub.10 -C.sub.20 alkyl sulfonates, C.sub.10 -C.sub.20 alkylene sulfonates, and mixtures thereof; and optionally at least one of: PA1 (b) 0.10-7.0 (more particularly 0.10-5.00) percent of a stabilizing agent selected from the group described above as stabilizing agents, particularly polyacrylic acid, derivatives of polyacrylic acid, acrylates copolymer, derivatives of acrylates copolymer, and polymeric emulsifiers such as acrylates/C10-30 alkyl acrylate crosspolymer, with particular products including products with brand names ACULYN.RTM. 33, TAB.RTM.-2, SAB-2 and PEMULEN.TM.; mixtures of ACULYN.RTM. 22 acrylates/steareth-20 methacrylate copolymer and the ACULYN.RTM. 33 product (such as in the range of about 50/50) may also be used; PA1 (c) optionally a quaternized cellulosic polymers (in particular at least one quaternized cellulosic polymer, for example, Polyquaternium-10); PA1 (d) the balance as water or aqueous medium. For conditioning shampoos, optionally another ingredient can be added as (e): PA1 (e) 0.01-10.00 percent of a water-insoluble conditioning agent which is selected from the group consisting of: PA1 (a) viscosity controlling agents for shampoos-polyvinyl alcohol, ethyl alcohol, acrylic acid polymers and copolymers, cellulosic ethers, diethanolamide or monoethanolamide of a long chain fatty acid (for example, PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide, sodium chloride, sodium sulfate, water soluble polymers (such as guar gum) particularly a thickening agent such as hydroxypropylcellulose, guar hydroxypropyltrimonium chloride, PEG-120 methyl glucose dioleate, pentaerythrityl tetrastearate, and xanthan gum. PA1 (a1) viscosity controlling agents for conditioners--polyvinyl alcohol, ethyl alcohol, cellulosic ethers, polyacrylamides, water soluble polymers (such as hydroxyethylcellulose, guar gum, and starch) particularly a thickening agent such as hydroxyethylcellulose, and guar hydroxypropyltrimonium chloride. PA1 (b) fragrances (perfumes) such as cosmetically acceptable fragrances used in hair care products; PA1 (c) preservatives, for example, antimicrobial agents, particularly a mixture of methylchloromethylisothiazolinone and methylisothiazolinone (sold under the tradename KATHON.RTM. CG by Rohm and Haas, Philadelphia, Pa.) but also including benzyl alcohol, ethyl paraben, propyl paraben and imidazolidinyl urea, DMDM hydantoin, formalin, 2-bromo-2-nitropropane-1,3-diol ("Bronopol"), and combinations of the foregoing. Particular examples may also include a potentiator such as ethylenediamine tetraacetic acid or the sodium salt form, (for example, Bronopol and EDTA (such as 0.04% Bronopol and 0.1% EDTA); formalin, DMDM hydantoin and EDTA (such as 0.1% formalin, 0.45% DMDM hydantoin, and 0.2% EDTA)); PA1 d) dyes or coloring agents, pearlizers (such as ethylene glycol distearate, sodium octyl sulfate, titanium dioxide, or mica), and opacifying agents (such as glycol distearate, fatty ethoxylates, latex opacifiers, stearamide monoethanolamine (MEA) stearate, sodium cetyl stearate and lanolin derivatives) suitable for use in hair care products; PA1 (e) pH adjusting agents such as citric acid, sodium carbonate, etc.; PA1 (f) sequestering agents such as ethylene diamine tetraacetic acid and sodium salts of the foregoing. Such additives may be included on an individual basis in appropriate amounts, for example in the range of about 0.01%-60%, preferably from abut 0.5%-40% by weight of the total weight of the composition.
U.S. Pat. No. 4,902,499 to Bolich et al teaches hair care compositions which give both improved style retention and hair conditioning. The compositions comprise 0.01-10% of a rigid silicone polymer and a volatile carrier. Suitable polymers include filler reinforced polydimethyl siloxane gums, cross-linked siloxanes, organic substituted siloxane gums, resin reinforced siloxanes and cross-linked siloxane polymers.
European Patent Application EP 0 0240 350 B1 to Snyder et al claims the use of compositions having style retention and hair conditioning properties wherein the composition comprises (a) a rigid silicone polymer having a complex viscosity of at least 1.times.10.sup.6 Pascal seconds (1.times.10.sup.7 poise) selected from the group consisting of organic substituted siloxane gums, silicone elastomers, filler reinforced polydimethyl siloxane gums, resin reinforced siloxanes and cross-linked siloxane polymers; and (b) a volatile carrier selected from water, straight chain or branched C10-C16 volatile hydrocarbons, and volatile silicones having a boiling point in the range of 99-260 degrees C, wherein if water is the sole carrier, from 0.05-50% by weight of a surfactant is also present and wherein is excluded the use of a silicone polymer in the manufacture of an aqueous aerosol hair styling mousse composition wherein the silicone polymer is in the form of an emulsion comprising an anionically stabilized hydroxylated polyorganosiloxane.
Other attempts have included the creation of hair thickeners. PCT Patent Application Publication Number WO 96/38120 to Grossman describes a hair thickener and conditioning gelatin composition for topical application to the hair. A formulation comprising an aqueous gelatin solution, a water-soluble film-forming polymer, and an acid neutralizing agent to maintain the pH of the composition in the range of 6.0-9.5 is disclosed. The types of water-soluble, film-forming polymers suitable for us with this composition include polyvinyl pyrrolidone (PVP), polyvinyl acetate, partially hydrolyzed polyvinyl acetate, copolymers of PVP and vinyl acetate, polyvinyl alcohol, acrylate-acrylamide copolymers, acrylate-PVP copolymers and the like, wherein the polymers have a number average molecular weight ranging between 5,000-10,000 daltons.
Siloxane resins consisting of triorganosiloxane units and silicon dioxide units are known, commercially available materials and are employed in the formulation of various products including adhesives, anti-foaming agents as well as personal care products; however, it is not believed that these compounds have been used commercially in hair care products of the type described here. Such resins are sometimes referred to as "MQ resins" because of the presence of the monovalent (M) siloxane units and the quadrivalent or tetravalent (Q) silicon dioxide units.
In view of the reactivity of the silyl hydride group, it is sometimes desired to include such groups in MQ type resins. Siloxane resins composed of silicon dioxide units and units of the general formula H.sup.1 R.sup.2 SiO.sub.1/2, where each of R.sup.1 and R.sup.2 may be the same or different and each is selected from hydrogen, a monovalent hydrocarbon and a monovalent halohydrocarbon are frequently used because of the high reactivity of the silyl hydride functionality therein. Such resins have been used for organopolysiloxane elastomers. As precursors to other synthetic silicones, it is frequently desirable that these resins contain a limited number of silyl groups. U.S. Pat. No. 3,772,247 discloses organopolysiloxane resins consisting of R.sup.3 R.sup.4 R.sup.5 SiO.sub.1/2 units, SiO.sub.2 units and units of the type HR.sup.3 SiO and/or HSiO.sub.3/2 in which each of R.sup.3, R.sup.4, and R.sup.5 are independently selected from the group consisting of alkyl, aryl, alkaryl, alkenyl, cycloalkyl and cycloalkenyl groups. While such resins possess silyl hydride groups, they possess a significant and measurable level of divalent or trivalent organosiloxyl groups.
U.S. Pat. No. 4,774,310 to Butler discloses MQ resins consisting of R.sup.3 R.sup.4 R.sup.5 SiO.sub.1/2 units and SiO.sub.2 units where R.sup.3, R.sup.4, and R.sup.5 are independently selecte from the group consisting of alkyl, aryl, alkaryl, alkenyl, cycloalkyl and cycloalkenyl groups. The MQ resins of this reference are further reacted with disiloxanes using acidic catalysis to product MQ type siloxane resins where the M:Q ratio is in the range of 0.4:1to 1:1, and where the fraction of hydride stopped units of the general formula H.sub.a R.sup.n.sub.3-a SiO.sub.1/2, where R.sup.n is selected from the same group as defined for R.sup.3, R.sup.4, and R.sup.5 is in the range of 0.1-30 percent of the total number of M units present.
British Patent 2,297,757 to Berthiaume et al describes low viscosity organofunctionalized siloxysilicates which are of the "MQ" type and which are stated as being useful as cosmetic and personal care products. These functionalized MQ silicone resins have the general formula: ##STR1##
where both R.sup.1 and R.sup.2 may be either a phenyl group or a C1-C12 alkyl group and both M.sup.1 and M.sup.2 are independently selected from the group consisting of phenyl, phenethyl, polyether, hydrogen and C1-C23 alkyl group (which may also include halogen substituted hydrocarbon radicals) and wherein x, y and z satisfy the following relationship: 0.5.ltoreq.(x+y)/z.ltoreq.4.0 and one of x and y may be zero.
U.S. Pat. No. 5,585,094 to Villamarin discloses a method for semi-permanently conditioning the hair wherein a low viscosity oil-in water emulsion of a mixture of two polysiloxane polymers is applied (one being a hydroxy terminated dimethyl polysiloxane and the other being a methyl hydrogen polysiloxane) at an acid pH and in an unreacted state. Preferably heat is applied to crosslink the polymers.
U.S. Pat. No. 4,963,348 to Bolich et al describes styling agents and compositions comprising adhesive copolymers with a volatile diluent to provide hair styling and hold.
There still remains a need, however, to provide compositions suitable for use as hair volumizers which do not leave the hair stiff or excessively sticky.
Thus, it is an object of the present invention to provide volumizing compositions that do not rely on sticking hair fibers together to achieve volume increases. In particular, it is an important object of this invention to provide a hair volumizer which is capable of giving volume to hair without substantial adhesion between the hair fibers. It is a further object of the invention to provide a hair volumizer which allows the hair to be manipulated and re-volumized between washings. It is also an object of the present invention to provide compositions suitable for use as hair volumizers which are useful to increase hair volume by a substantial amount. It is yet another object of the present invention to provide compositions suitable for use as hair volumizers which use MQ resins and which allow the hair to withstand compression of the hair network. These and other objects of the invention will become apparent from the following description.